CN111162316B - Non-aqueous electrolyte and secondary lithium battery - Google Patents
Non-aqueous electrolyte and secondary lithium battery Download PDFInfo
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- CN111162316B CN111162316B CN201811324717.6A CN201811324717A CN111162316B CN 111162316 B CN111162316 B CN 111162316B CN 201811324717 A CN201811324717 A CN 201811324717A CN 111162316 B CN111162316 B CN 111162316B
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- carbonate
- electrolyte
- electrolytic solution
- nonaqueous electrolytic
- lithium battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a non-aqueous electrolyte, which comprises lithium salt, an organic solvent and a functional additive, wherein the functional additive comprises a triphenylphosphine derivative, and the general structural formula of the triphenylphosphine derivative is as follows:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, alkenyl, haloalkenyl, phenyl, halophenyl, biphenyl, halophenyl, phenyl ether, triphenyl, halophenyl ether, amino, ester or cyano, wherein the halogen is F, Cl or Br, and the halogen is partially or fully substituted. The electrolyte can well inhibit the dissolution of metal ions in the anode material, protect the anode, effectively reduce the thickness expansion of the lithium battery and improve the capacity retention rate of the secondary lithium battery.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a non-aqueous electrolyte and a secondary lithium battery.
Background
With the rapid development of portable electronic devices, hybrid vehicles, electric vehicles, space technology, and the like, secondary batteries have raised higher requirements in terms of specific capacity, cycle life, safety, and the like. Currently, lithium ion battery anode materials widely used in practice are lithium cobaltate, lithium manganate, lithium iron phosphate and the like. And with the progress of the charge-discharge cycle of the battery, metal ions in the anode material are dissolved out into the electrolyte, and the reaction of the anode active substance and the electrolyte is accelerated, so that the battery has serious ballooning in the cycle process, obvious battery capacity attenuation and reduced cycle performance, and the performance of the anode material is seriously restricted.
Disclosure of Invention
The present invention addresses the problem of providing a nonaqueous electrolytic solution and a secondary lithium battery that can suppress elution of metal ions from a positive electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
one object of the present invention is to provide a nonaqueous electrolytic solution, which comprises a lithium salt, an organic solvent and a functional additive, wherein the functional additive comprises a triphenylphosphine derivative, and the triphenylphosphine derivative has a general structural formula:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, alkenyl, haloalkenyl, phenyl, halophenyl, biphenyl, halophenyl, phenyl ether, triphenyl, halophenyl ether, amino, ester or cyano, wherein the halogen is F, Cl or Br, and the halogen is partially or fully substituted.
Preferably, R 1 、R 2 、R 3 Independently hydrogen, hydroxyl, halogen, alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms, halogenated alkyl with 1-5 carbon atoms, halogenated alkoxy with 1-5 carbon atoms, alkene with 2-5 carbon atoms, halogenated alkene with 2-5 carbon atoms, phenyl, halogenated phenyl, biphenyl, halogenated biphenyl, phenylether group, triphenyl, halogenated phenylether group, halogenated triphenyl, amino, ester group or cyano.
Further preferably, R 1 、R 3 Independently of one another is hydrogen, R 2 Is an ester group.
Most preferably, the triphenylphosphine derivative is
Preferably, the mass of the triphenylphosphine derivative is 0.05-10% of the total mass of the nonaqueous electrolyte.
More preferably, the mass of the triphenylphosphine derivative is 0.1-5% of the total mass of the nonaqueous electrolyte.
More preferably, the mass of the triphenylphosphine derivative is 0.1-2% of the total mass of the nonaqueous electrolyte.
Most preferably, the mass of the triphenylphosphine derivative is 0.1-0.5% of the total mass of the nonaqueous electrolyte.
Preferably, the lithium salt is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiCH 3 SO 3 、LiSCN、LiNO 3 、LiO 3 SCF 2 CF 3 、LiAsF 6 、LiAlCl 4 One or more of (a).
Preferably, the concentration of the lithium salt in the nonaqueous electrolytic solution is 0.7 to 1.5 mol/L.
More preferably, the concentration of the lithium salt in the nonaqueous electrolytic solution is 0.9 to 1.2 mol/L.
Preferably, the organic solvent is one or more selected from carbonates, carboxylates, ethers, sulfones.
In the present invention, when two or more organic solvents are mixed, the organic solvents may be in any weight ratio.
Preferably, the carbonate is a cyclic carbonate and/or a chain carbonate, and when the cyclic carbonate and the chain carbonate are used simultaneously, the cyclic carbonate and the chain carbonate may be in any weight ratio.
Further preferably, the carbonate is one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propylene carbonate.
More preferably, the organic solvent is a mixed solvent of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and propylene carbonate in a mass ratio of 2-6: 5-11: 1-2: 1.
Most preferably, the organic solvent is a mixed solvent of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and propylene carbonate in a mass ratio of 5-6: 10-11: 1.5-2: 1.
Preferably, the carboxylic ester is a cyclic carboxylic ester and/or a chain carboxylic ester, and when the cyclic carbonate and the chain carbonate are used simultaneously, the mass ratio of the cyclic carboxylic ester to the carboxylic ester is 1: 0.5-2.5.
Further preferably, the carboxylic ester is one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate and ethyl butyrate.
Further preferably, the ether is one or more of dimethoxymethane, 1, 2-dimethoxyethane, tetrahydrofuran and 1, 3-dioxolane.
Further preferably, the sulfone is one or more of dimethyl sulfoxide, sulfolane and dimethyl sulfone.
It is another object of the present invention to provide a secondary lithium battery using the nonaqueous electrolytic solution.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the electrolyte can well inhibit the dissolution of metal ions in the anode material, protect the anode, effectively reduce the thickness expansion of the lithium battery and improve the capacity retention rate of the secondary lithium battery.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. In this specification, "%" represents mass% unless otherwise specified.
Comparative example 1
Lithium salt LiPF 6 Dissolved in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio of 25/50/15/10), wherein LiPF 6 The concentration was 1mol/L, giving a comparative electrolyte.
Example 1
Lithium salt LiPF 6 Dissolved in ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/carbonic acid Propylene ester (mass ratio 30/55/10/5), wherein LiPF 6 The concentration is 1mol/L, and 0.1 percent of the total electrolyte mass is added into the solution
The electrolyte of the invention is obtained.
Example 2
Lithium salt LiPF 6 Dissolving in mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio 30/55/10/5), wherein LiPF 6 The concentration is 1mol/L, and 0.2 percent of the electrolyte is added into the solution according to the total mass of the electrolyte
The electrolyte of the invention is obtained.
Example 3
Lithium salt LiPF 6 Dissolved in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio of 30/55/10/5), wherein LiPF 6 The concentration is 1mol/L, and 0.5 percent of the electrolyte is added into the solution according to the total mass of the electrolyte
The electrolyte of the invention is obtained.
Example 4
Lithium salt LiPF 6 Dissolved in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio of 30/55/10/5), wherein LiPF 6 1mol/L of the electrolyte solution, and 1 percent of the electrolyte solution is added into the electrolyte solution according to the total mass of the electrolyte solution
The electrolyte of the invention is obtained.
Example 5
Lithium salt LiPF 6 Dissolved in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio of 30/55/10/5), wherein LiPF 6 The concentration is 1mol/L, and 2 percent of the electrolyte is added into the solution according to the total mass of the electrolyte
The electrolyte of the invention is obtained.
Example 6
Lithium salt LiPF 6 Dissolved in a mixed solvent of ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate/propylene carbonate (mass ratio of 30/55/10/5), wherein LiPF 6 The concentration is 1mol/L, and 5 percent of the electrolyte solution is added into the solution according to the total mass of the electrolyte
The electrolyte of the invention is obtained.
Results of the experiment
The electrolyte obtained in the comparative example 1 and the electrolyte obtained in the examples 1 to 6 are injected into lithium cobaltate soft package batteries of the same batch and the same model, and the test batteries are subjected to 1C cycle performance test in a normal temperature environment of 2.75-4.2V. The normal-temperature cycle capacity retention rate and the thickness comparison data before and after the cycle of all the comparative examples and the examples have the following specific results:
TABLE 1
The data of the charge-discharge cycle performance test of the lithium cobaltate batteries prepared by the non-aqueous electrolyte of each example and the comparative example in the table 1 show that the cycle life of the lithium cobaltate battery prepared by the non-aqueous electrolyte of the invention is obviously better than that of the lithium cobaltate battery prepared by the non-aqueous electrolyte of the comparative example in the range of 2.75-4.2V and 1C multiplying power charge-discharge and the expansion rate of the battery thickness. In addition, example 2 above is very advantageous in terms of the cycle retention of the battery, the degree of swelling of the battery, and the suppression of elution of metal ions.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (6)
1. A non-aqueous electrolyte comprising a lithium salt, an organic solvent and a functional additive, wherein: the functional additive comprises a triphenylphosphine derivative
(ii) a The feeding mass of the triphenylphosphine derivative is 0.05-10% of the total mass of the nonaqueous electrolyte.
2. The nonaqueous electrolytic solution of claim 1, wherein: the lithium salt is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiCH 3 SO 3 、LiSCN、LiNO 3 、LiO 3 SCF 2 CF 3 、LiAsF 6 、LiAlCl 4 The concentration of the lithium salt in the nonaqueous electrolytic solution is 0.7 to 1.5 mol/L.
3. The nonaqueous electrolytic solution of claim 1, wherein: the organic solvent is one or more selected from carbonate, carboxylate, ether and sulfone.
4. The nonaqueous electrolytic solution of claim 3, wherein: the carbonate is cyclic carbonate and/or chain carbonate.
5. The nonaqueous electrolytic solution of claim 4, wherein: the carboxylic ester is cyclic carboxylic ester and/or chain carboxylic ester.
6. A secondary lithium battery characterized in that: the nonaqueous electrolytic solution according to any one of claims 1 to 5 is used.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811324717.6A CN111162316B (en) | 2018-11-08 | 2018-11-08 | Non-aqueous electrolyte and secondary lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811324717.6A CN111162316B (en) | 2018-11-08 | 2018-11-08 | Non-aqueous electrolyte and secondary lithium battery |
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| CN111162316B true CN111162316B (en) | 2022-07-29 |
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| CN113745661B (en) * | 2021-11-08 | 2022-03-18 | 河南电池研究院有限公司 | High-voltage electrolyte matched with ternary cathode material lithium ion battery |
| CN114243113A (en) * | 2021-12-27 | 2022-03-25 | 天津中电新能源研究院有限公司 | High-temperature electrolyte additive, battery electrolyte and sodium ion battery |
| CN115505115B (en) * | 2022-11-21 | 2023-03-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Composition for preparing gel electrolyte, electrolyte and battery thereof |
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| KR100477751B1 (en) * | 2002-11-16 | 2005-03-21 | 삼성에스디아이 주식회사 | Non-aqueous electrolyte and lithium battery employing the same |
| KR100713622B1 (en) * | 2006-01-09 | 2007-05-02 | 제일모직주식회사 | Nonaqueous electrolyte including diphenyl ether and lithium secondary battery using thereof |
| CN103840210B (en) * | 2012-11-26 | 2016-06-29 | 华为技术有限公司 | A kind of non-water organic electrolyte and preparation method thereof and lithium rechargeable battery |
| CN106532117A (en) * | 2016-11-17 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| US10461364B2 (en) * | 2017-04-20 | 2019-10-29 | Uchicago Argonne, Llc | Electrolyte additives for lithium-ion batteries under high-voltage operation |
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